Agent for dyeing fibers comprising an indoline/indolium derivative

ABSTRACT

The object of the present invention is an agent for dyeing fibers obtained by mixing two components and characterized in that one component (component A2) contains at least one carbonyl compound and the other component (component A1) contains at least one indoline derivative of formula (I) or a 3H-indoline derivative of formula (Ia)  
                 
 
     as well as a multicomponent kit for dyeing and later decolorizing fibers, said kit containing both an agent according to the invention for producing a coloration on the fiber and an agent for the reductive removal of said coloration.

[0001] The object of the present invention is an agent for dyeingfibers, particularly keratin fibers (for example human hair), said agentcontaining an indole derivative and a carbonyl compound, and to amulticomponent kit for dyeing and subsequently decolorizing fibers, saidkit containing both an agent for producing a coloration on the fibersand an agent for the reductive removal of the coloration.

[0002] Depending on the starting color of the hair to be dyed and thedesired end result, hair colorants fall mainly into the domain ofoxidative hair dyes and tinting agents. Oxidative dyes lend themselveseminently to the covering of large gray areas. The oxidative dyes usedwhen the gray area amounts to up to 50% are usually referred to asoxidative tinting agents, whereas the oxidative dyes used when the grayarea exceeds 50% or the dyes used for “bright coloring” are usuallyreferred to as oxidative dyes. Direct dyes are contained mainly innon-oxidative colorants (tinting agents). Some direct dyes, for examplethe nitro dyes, can, because of their small size, penetrate into thehair and—at least in the outer regions—bring about direct dyeing. Suchtinting agents are very gentle to the hair, they can usually withstand 6to 8 hair washings and they allow a gray coverage of about 20%.

[0003] In general, direct dyes and oxidative tints are washed out of thehair after a few hair washings. Their durability depends among otherthings on the hair structure and the color shade used. Oxidative dyescan fade somewhat with time, but as a rule remain on the hair until thenext haircut. When it is desired to wear a particular color only for acertain length of time or if the user dislikes a color, however, it maybe desirable to be able to remove the hair coloring at any time. Also,when a person's hair is dyed for the first time, a gentle and completeremoval of the coloration can reduce the fear of an excessively drasticcolor change (“test dyeing”).

[0004] European Patent EP 0 847 749 discloses a combination ofdiiminoisoindoline or 3-aminoisoindolone derivatives and compounds withprimary or secondary amino groups for coloring keratin fibers withoutthe addition of an oxidant. It Is also known from German UnexaminedPatent Application DE-OS 43 35 623 to use for the dyeing of keratinfibers a combination of indolinone derivatives and compounds withprimary or secondary amino groups, heterocycles or aromatic hydroxycompounds. Moreover, DE-OS 44 09 143 describes the use of isatinderivatives for the dyeing of keratin fibers. DE-OS 197 45 292 disclosesthe use of a combination of malonaldehyde derivatives, for examplemalonaldehyde-bis-dialkyl acetals, and amines or CH-acidic compounds fordyeing hair without the addition of oxidants. Also, DE-OS 197 17 280discloses the use of a combination of certain heterocyclic aldehydes andamines or CH-acidic compounds for dyeing hair without the addition ofoxidants.

[0005] A great demand, however, continues to exist for colorants whichunder mild conditions give intense as well as gentle colorations in awide range of shades and which—if desired—can subsequently be removed atany time.

[0006] The object of the present invention is therefore to provide adyeing system which without the addition of an oxidant (for examplehydrogen peroxide) gives a gentle, intense coloration on fibers in theyellow, brown, green and purple range with good fastness properties(light fastness, wash fastness, abrasion resistance) and at the sametime permits gentle and complete removal of said coloration at any pointin time.

[0007] Surprisingly, we have now found that dyes containing an indolinederivative of formula (I) or a 3H-indolium derivative of formula (Ia) aswell as a carbonyl compound give in gentle manner intense colorationswhich can be removed completely at any desired subsequent point in time.

[0008] Hence, the object of the present invention is an agent for dyeingfibers, for example wool, silk, cotton or hair, and particularlykeratinic fibers, for example human hair, said agent being obtained bymixing two components—if necessary with addition of an alkalinizingagent or an acid—and being characterized in that one component(component A2) contains at least one carbonyl compound, particularly anaromatic aldehyde compound, and the other component (component A1)contains at least one indoline derivative of formula (I) or a3H-indolium derivative of formula (Ia)

[0009] the R1 to R8 and A⁻ groups in formulas (I) and (Ia) having thefollowing meaning:

[0010] R1 denotes a straight-chain or branched C1-C8 alkyl group, C1-C8monohydroxyalkyl group, C2-C8 polyhydroxyalkyl group, C1-C8alkoxy-(C1-C8)-alkyl group or a thio-(C1-C8)-alkyl group, a—(CH₂)_(m)—X—(CH₂)_(n)—Y—(CH₂)_(p)—R^(a) group, a —(CH₂)_(n)—X—R^(a)group, a —(CH₂)_(m)—Y—(CH₂)_(n)—X—(CH₂)_(p)—R^(a) group, a—(CH₂)_(m)—CO—(CH₂)_(p)—X—R^(a) group, a —(CH₂)_(p)—R^(a) group, a—(CH₂)_(m)—X—(CH₂)_(p)—CO—Y—R^(a) group or

[0011]  wherein

[0012] X and Y independently of each other denote an oxygen atom, asulfur atom or an NR^(b) group, R^(a) and R^(b) independently of eachother denote a hydrogen atom, an, optionally substituted, aromaticcarbocycle or heterocycle or a straight-chain or branched C1-C8 alkylgroup, m and n independently of each other denote an integer from 1 to 6and p denotes an integer from 0 to 6;

[0013] R2 is a hydrogen atom or a straight-chain C1 to C6-alkyl group,

[0014] R3 and R4 independently of each other denote a straight-chain orbranched C1-C4-alkyl group (particularly a methyl group), a(CH₂)_(n)—R^(c) group, a —(CH₂)_(m)—CHR^(c)—X—(CH₂)_(n)—R^(c) group, a—(CH₂)_(n)—CO—R^(c) group, a —(CH₂)_(n)—CO—XR^(c) group, a (CH₂)_(n)—CNgroup, a —(CH₂)_(n)—CH═C(CH₃)₂ group, a—(CH₂)_(m)—X—CHR^(c)—(CH₂)_(n)—R_(c) group or a —(CH₂)_(n)CH═CH group, Xstanding for an oxygen atom, a sulfur atom or an NR^(b) group, m and nindependently of each other denoting 1 to 6 and R^(c) standing for ahydrogen atom, an, optionally substituted, aromatic carbocycle orheterocycle or a straight-chain or branched C1-C6-alkyl group, providingthat the R3 and R4 groups, together, linked through a (CH₂)_(n) group(with n=1-3) can also form a spiro compound with the 3H carbon;

[0015] R5, R6, R7 and R8 independently of each other denote astraight-chain or branched C1-C4-alkyl group or a C1-C4-hydroxyalkylgroup, a hydroxyl group, a methoxy group, a benzyl group, a halogen atom(F, Cl, Br, I), a nitro group, a nitroso group, a cyano group, atrifluoromethyl group, a —CHO group, a —COR^(d) group, a —COOH group, a—CO₂R^(d) group, an —OCOR^(d) group, an —OCH₂-aryl group, an —SO₂NH₂group, an —NH₂ group, an —NH₃ ⁺ group, an —NHR^(d) group, an —NH₂R^(d+)group, an —N(R^(d))₂ group, an —N(R^(d))₃ ⁺ group, an —NHCOR^(d) group,an —NHCOOR^(d) group, a —CH₂NH₂ group, a —CH₂NHR^(d) group, a—CH₂N(R^(d))₂ group, a —CO₂CF₃ group, a —PO(OR^(d))₂ group, —SO₂CHF₂group, an —SO₂CF₃ group an —SO₂R^(d) group or an —SR^(d) group, whereinR^(d) denotes a hydrogen atom, an, optionally substituted, aromaticcarbocycle or a heterocycle or a C1-C6-alkyl group, providing that atleast one of the R5 to R8 groups is different from hydrogen; and

[0016] A⁻ denotes an anion of an organic or inorganic acid.

[0017] A⁻ is preferably a chloride, bromide, iodide, hydrogen sulfate,sulfate, toluenesulfonate, benzenesulfonate, monomethyl sulfate,hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate,tetraphenylborate, formate, acetate or propionate ion. The chloride ion,tetrafluoroborate ion, acetate ion and hydrogen sulfate ion areparticularly preferred.

[0018] Among the compounds of formulas (I) and (Ia), the following arepreferred:

[0019] 1,3,3,4-tetramethyl-2-methyleneindoline and the salts thereof,

[0020] 1,3,3,5-tetramethyl-2-methyleneindoline and the salts thereof,

[0021] 1,3,3,6-tetramethyl-2-methyleneindoline and the salts thereof,

[0022] 1,3,3,7-tetramethyl-2-methyleneindoline and the salts thereof,

[0023] 1,3,3,6,7-pentamethyl-2-methyleneindoline and the salts thereof,

[0024] 1,3,3,5,7-pentamethyl-2-methyleneindoline and the salts thereof,

[0025] 1,3,3,4,7-pentamethyl-2-methyleneindoline and the salts thereof,

[0026] 5-fluoro-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0027] 5-isopropyl-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0028] 5-hydroxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0029] 5-methoxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0030] 5-nitro-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0031] 5-amino-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0032] 5-N-acetylamino-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0033] 6-hydroxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0034] 6-methoxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0035] 5-methoxy-6-nitro-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof,

[0036] 5-methoxy-6-amino-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof,

[0037] 5-methoxy-6-N-acetylamino-1,3,3-trimethyl-2-methyleneindoline andthe salts thereof,

[0038] 5,6-dihydroxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0039] 5,6-dimethoxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0040] 5,6-methylenedioxy-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof,

[0041] 4,5-dihydroxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0042] 5,7-dihydroxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof,

[0043] 5-amino-6-methoxy-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof,

[0044] 5-amino-7-hydroxy-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof,

[0045] 5-hydroxy-7-amino-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof,

[0046] 5-hydroxy-7-N-acetylamino-1,3,3-trimethyl-2-methyleneindoline andthe salts thereof,

[0047] 1-methyl-3-spirocyclopropyl-2-methyleneindoline and the saltsthereof,

[0048] 1-methyl-3-spirocyclohexyl-2-methyleneindoline and the saltsthereof,

[0049] 1-methyl-3-spirocyclohexyl-5-hydroxy-2-methyleneindoline and thesalts thereof,

[0050] 1-methyl-3-spirocyclohexyl-5-methoxy-2-methyleneindoline and thesalts thereof,

[0051] the following being particularly preferred:

[0052] 1,2,3,3,5-pentamethyl-3H-indolium iodide,

[0053] 1,2,3,3,7-pentamethyl-3H-indolium tetrafluoroborate,

[0054] 1,2,3,3,6,7-hexamethyl-3H-indolium tetrafluoroborate,

[0055] 1,2,3,3,5,7-hexamethyl-3H-indolium tetrafluoroborate,

[0056] 1,2,3,3,4,7-hexamethyl-3H-indolium tetrafluoroborate,

[0057] 5-fluoro-1,2,3,3-tetramethyl-3H-indolium iodide,

[0058] 5-isopropyl-1,2,3,3-tetramethyl-3H-indolium iodide,

[0059] 5-nitro-1,3,3-trimethyl-2-methyleneindoline

[0060] and especially

[0061] 5-methoxy-1,2,3,3-tetramethyl-3H-indolium iodide,

[0062] 5-methoxy-6-nitro-1,2,3,3-tetramethyl-3H-indolium chloride,

[0063] 5-hydroxy-1,2,3,3-tetramethyl-3H-indolium iodide and

[0064] 5-N-acetylamino-1,2,3,3-tetramethyl-3H-indolium acetate.

[0065] The compounds of formulas (I) and Ia) used according to theinvention are known from the literature or can be prepared by standardmethods of synthesis known from the literature, for example such asthose described in the dissertation by Andreas Leiminer, University ofRegensburg (1995); in the German Unexamined Patent Application [DE-OS] 1949 716 or in U.S. Pat. No. 3,865,837. By the electrophilic substitutionreactions known from the literature, additional, new substituents, forexample a nitro function, can be introduced into the aromatic ring. Inthis respect, the reader is referred particularly to the synthesismethod described by D. J. Gale and J. F. K. Wilshire in J. Soc. DyersColour; 1974. pp. 97-100. By later treatment with reducing or oxidizingagents or with the aid of appropriate protective group addition orelimination reactions, the functional nature of the introducedsubstituents can be modified whereby additional compounds of generalformulas (I) and (Ia) can be obtained.

[0066] Suitable carbonyl compounds are, in particular, the followingaldehydes: vanillin (4-hydroxy-3-methoxybenzaldehyde), isovanillin(3-hydroxy-4-methoxybenzaldehyde), 3,4-dihydroxybenzaldehyde,4-hydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde,4-dimethylaminobenzaldehyde, 4-methyl-5-imidazolecarboxaldehyde,4-dimethylaminocinnamaldehyde, 4-hydroxy-2-methoxybenzaldehyde,3,5-dimethyl-4-hydroxybenzaldehyde,4-dimethylamino-2-methoxybenzaldehyde, 2-hydroxybenzaldehyde,4-hydroxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde,4-dimethylamino-1-naphthaldehyde, 4′-hydroxybiphenyl-1-carboxaldehyde,2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde,3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde,2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde,2,4,6-trihydroxybenzaldehyde, 2,4-dimethoxybenzaldehyde,2,3-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde,3,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde,indole-3-carboxaldehyde, benzene-1,4-dicarboxaldehyde,4-ethoxybenzaldehyde, 2-methyl-1,4-naphthoquinone,4-carboxybenzaldehyde, 4-hydroxy-3-methoxycinnamaldehyde,3,5-dimethoxy-4-hydroxycinnamaldehyde,3-methoxy-4-(1-pyrrolidinyl)benzaldehyde,4-diethylamino-3-methoxybenzaldehyde, 1,2,-phthalaldehyde,pyrrole-2-aldehyde, thiophene-2-aldehyde, thiophene-3-aldehyde,chromone-3-carboxaldehyde, 6-methyl-4-oxo-1(4H)-benzopyran-3-carboxaldehyde, N-methylpyrrole-2-aldehyde,5-methylfufural, 6-hydroxychromene-3-carboxaldehyde,6-methylindole-3-carboxaldehyde, 4-dibutylaminobenzaldehyde,N-ethyl-carbazole-3-aldehyde, 4-diethylamino-2-hydroxybenzaldehyde,3,4-dimethoxy-5-hydroxybenzaldehyde,5-[4-(diethylamino)phenyl]-2,4-pentadienal, 2,3-thiophenecarboxaldehyde,2,5-thiophenedicarboxaldehyde, 2-methoxy-1-naphthaldehyde,3-ethoxy-4-hydroxybenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehydeand 4-nitrobenzaldehyde.

[0067] The compounds of formulas (I) and (Ia) are kept separated fromthe carbonyl compounds until shortly before use. As a rule, the colorantof the invention is a mixture of the two components A1 and A2, namely ofa dye carrier composition (A1) containing the compounds (I) and/or (Ia)and optionally a direct dye, and an additional dye carrier composition(A2) containing the carbonyl compound and optionally a direct dye. Thesetwo components are mixed just before use to give a ready-for-usecolorant which is then applied to the fibers to be dyed. One or bothcomponents can, of course, also consist of several individual componentswhich are mixed with each other just before use.

[0068] The compounds of formulas (I) and (Ia) and the carbonyl compoundsare contained in each of the dye carrier compositions (component A1 orcomponent A2) in a total amount from about 0.02 to 20 wt. % andpreferably from 0.2 to 10 wt. %, and the ready-for-use colorant obtainedby mixing components A1 and A2 contains the compounds of formulas (I)and (Ia) and the carbonyl compound in a total amount from about 0.01 to10 wt. % and preferably from 0.1 to 5 wt. %.

[0069] Moreover, the coloring agent of the invention can optionallycontain common physiologically tolerated direct dyes from the group ofnitro dyes, azo dyes, quinone dyes and triphenylmethane dyes.

[0070] The direct dyes can be contained in each of component A1 andcomponent A2 in a total amount from about 0.2 to 10 wt. % and preferablyfrom about 0.02 to 10 wt. %, the total amount of direct dyes in theready-for-use colorant obtained by mixing components A1 and A2 beingfrom about 0.01 to 10 wt. % and preferably from 0.1 to 5 wt. %.

[0071] The ready-for-use colorant and components A1 and A2 can beprepared in the form of, for example, a solution, particularly anaqueous or aqueous-alcoholic solution. Other suitable forms are creams,gels, aerosol foams or emulsions. The colorant composition is a mixtureof the compounds of formulas ID (I) and (Ia) and/or a carbonyl compoundwith additives commonly used for such preparations.

[0072] Common additives used in colorants in the form of a solution,cream, emulsion, gel or aerosol foam are, for example, solvents such aswater, lower aliphatic alcohols, for example ethanol, n-propanol andisopropanol, or polyols such as glycerol and 1,2-propanediol, moreoverwetting agents or emulsifiers from the classes of anionic, cationic,amphoteric or nonionic surface-active agents, such as fatty alcoholsulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates,alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines,ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acidalkanolamides, ethoxylated fatty esters, furthermore thickeners such ashigher fatty alcohols, starch or cellulose derivatives, perfumes, hairpretreatment agents, conditioners, hair swelling agents, preservatives,moreover vaselines, paraffin oils and fatty acids as well as hair-careagents, such as cationic resins, lanolin derivatives, cholesterol,pantothenic acid and betaine. The aforesaid components are used inamounts commonly employed for such purposes, for example the wettingagents and emulsifiers at a concentration of about 0.5 to 30 wt. %(based on the dye carrier composition), the thickeners in an amount ofabout 0.1 to 25 wt. % (based on the dye carrier composition) and thehair-care agents at a concentration of about 0.1 to 5.0 wt. % (based onthe dye carrier composition).

[0073] As a rule, the pH of the ready-for-use colorant is about 3 to 11and preferably 6 to 11, a pH of 6.5 to 8.5 being particularly preferred.The pH of the ready-for-use colorant obtained by mixing theenamine-containing component A1 with the carbonyl-containing componentA2 depends on the pH of components A1 and A2 and on the mixing ratio ofthese two components. If necessary, after mixing components A1 and A2the pH of the ready-for-use colorant can be adjusted to the desiredvalue by adding an alkalinizing agent or an acid.

[0074] Suitable for adjusting the pH of the ready-for-use colorant andof components A1 and A2 are alkalinizing agents such as, for example,alkanolamines, alkylamines, alkali metal hydroxides or ammoniumhydroxide, alkali metal carbonates or ammonium carbonate, or acids suchas, for example, lactic acid, acetic acid, tartaric acid, phosphoricacid, hydrochloric acid, citric acid, ascorbic acid and boric acid.

[0075] The ready-for-use colorant is prepared immediately before use bymixing component A1 containing the compounds of formulas (I) and (Ia)with component A2 containing the carbonyl compound (optionally withaddition of an alkalinizing agent or an acid) and is then applied to thefibers. Depending on the depth of shade, this mixture is allowed to actat a temperature from 20 to 50° C., preferably from 30 to 40° C., for 5to 60 minutes and preferably for 15 to 30 minutes. The fibers are thenrinsed with water and optionally washed with a shampoo.

[0076] The colorant of the invention permits gentle, uniform and lastingdyeing of the fibers, particularly keratin fibers, for example hair.Surprisingly, the resulting colorations can be removed at any timecompletely, quickly and gently by use of a reducing agent.

[0077] Another object of the present invention is therefore amulticomponent kit for dyeing and later decolorizing fibers, for examplewool, silk, cotton or hair and particularly human hair, said kit beingcharacterized in that it contains the dyeing agent (A) of the inventionand a decolorizing component (B), said component B containing as thedecolorizing agent at least one sulfite, for example ammonium sulfite,alkali metal sulfite or alkaline earth sulfite, and particularly sodiumsulfite or ammonium sulfite.

[0078] The total amount of sulfites in component B is from about 0.1 to10 wt. % and preferably from 2 to 5 wt. %.

[0079] The agent for decolorizing the fibers dyed with colorant A (inthe following referred to as “decolorizer”) can be in the form of anaqueous or aqueous-alcoholic solution, gel, cream, emulsion or foam, itbeing possible to package the decolorizer either in the form of aone-component preparation or in the form of a multicomponentpreparation. The decolorizer can be packaged in the form of a powder or,to avoid dusting, in the form of tablets, including effervescenttablets, or as a granulate. Before use, the decolorizer is prepared withcold or warm water, optionally with addition of one or more of theauxiliary agents indicated in the following. It is also possible,however, for these auxiliary agents (if they are in a solid form) to bealready contained in the decolorizing powder, decolorizing granulate oreffervescent tablets. By wetting the powder with an oil or wax, dustingcan be additionally reduced.

[0080] The decolorizer can also contain auxiliary agents, for example, asolvent such as water, a lower alcohol, for example ethanol, n-propanol,or isopropanol, a glycol ether or a polyol such as glycerol and,particularly 1,2-propanediol, furthermore a wetting agent or emulsifierfrom the classes of anionic, cationic, amphoteric or nonionicsurface-active agents, such as fatty alcohol sulfates, ethoxylated fattyalcohol sulfates, alkylsulfonates, alkylbenzenesulfonates,alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols,ethoxylated nonylphenols, fatty acid alkanolamides, ethoxylated fattyesters, furthermore thickeners such as higher fatty alcohols, starch orcellulose derivatives, perfumes, hair pretreatment agents, conditioners,hair swelling agents, preservatives, vaselines, paraffin oils and fattyacids as well as hair-care agents, such as cationic resins, lanolinderivatives, cholesterol, pantothenic acid and betaine.

[0081] The pH of the decolorizer is from about 3 to 8 and particularlyfrom 4 to 7. If necessary, the desired pH can be obtained by adjustmentwith a suitable acid, for example an α-hydroxycarboxylic acid such aslactic acid, tartaric acid, citric acid or malic acid, or phosphoricacid, acetic acid, glycolic acid, salicylic acid, glutathione orgluconolactone, or with an alkalinizing agent such as an alkanolamine,alkylamine, alkali metal hydroxide, ammonium hydroxide, alkali metalcarbonate, ammonium carbonate or alkali metal phosphate.

[0082] Depending on the color to be removed and the temperature (about20 to 50° C.), the exposure time to the decolorizer is from 5 to 60minutes and particularly from 15 to 30 minutes. The decolorizing processcan be accelerated by the action of heat. At the end of the exposure tothe decolorizer, the hair is rinsed with water and optionally washedwith a shampoo.

[0083] Although component B is well suited for decolorizing hair,particularly human hair, dyed with dye A, component B can in principlealso be used for decolorizing other natural or man-made fibers dyed withcolorant A, for example cotton, wool, silk, viscose, nylon and celluloseacetate.

[0084] The following examples will explain the object of the inventionin greater detail without limiting its scope to the examples.

EXAMPLES Examples 1.1 to 1.12 Synthesis of the Indole Derivatives ofFormula (I)/(Ia)

[0085] General Method of Synthesis

[0086] 1a) General Method for Preparing the 3H-Indole Derivatives ofFormula (I)/(Ia)

[0087] Dissolve the substituted arylhydrazine (1 equivalent) in ethanolat 25° C. Add 1.2 equivalents of the alkyl ketone and heat 3 hours atreflux. Cool to about 60° C. and to the resulting arylhydrazone solutionadd dropwise concentrated sulfuric acid, then heat for an additional 5hours at reflux. Cool the re-action solution to 25° C. and concentrateit under reduced pressure to half its original volume. Add distilledwater to this reaction solution and make it alkaline by addingfour-molar sodium hydroxide solution. Extract the resulting emulsionwith diethyl ether. Combine the organic phases, dry over Na₂SO₄, filterand concentrate. Purify the resulting oil by bulb-tube distillation.

[0088] 1b) General Method for the N-Alkylation of the 3H-IndoleDerivatives from Step 1a

[0089] Variant 1

[0090] Dissolve the intermediate obtained in 1a) (II equivalent) inchloroform and to the solution add methyl iodide (1.1 to 2.1equivalents). Stir the resulting solution at 25° C. for 24 hours underan argon atmosphere with exclusion of light. To this solution addtertbutyl methyl ether, collect the yellow precipitate by suctionfiltration and crystallize it from ethanol.

[0091] Variant 2

[0092] Stir a suspension of the intermediate obtained in 1a) (1equivalent) in methyl iodide (5 equivalents) for 4 hours with the aid ofultrasound (120 W). Filter off the solid formed, wash it with tert.butylmethyl ether and crystallize it from ethanol.

[0093] Variant 3

[0094] Dissolve the intermediate obtained in 1a) (1 equivalent) inmethanol, add methyl iodide (2 equivalents) and heat at reflux for 12hours while keeping the reaction solution protected from light and underan argon atmosphere. Evaporate the reaction solution to dryness underreduced pressure. Wash the residue with ethyl acetate and crystallize itfrom methanol.

[0095] Variant 4

[0096] Dissolve the intermediate obtained in 1a) (1 equivalent) in1,2-dichloroethane, add trimethyloxonium tetrafluoroborate (1.2equivalents) and heat at reflux for 6 hours. Precipitate the product bycooling the reaction mixture to 4° C. or by adding ethyl acetate. Filteroff the resulting solid, wash it with a small amount of ethyl acetateand crystallize it from methanol.

[0097] 1c) General Method for the Demethylation of the Aryl Methyl Ether

[0098] Dissolve the aryl methyl ether in acetic acid and add 48%hydrobromic acid solution. Heat the reaction mixture at reflux for 8hours, then allow it to agitate overnight at room temperature.Neutralize the reaction solution with 20% sodium hydroxide solution,render it alkaline with saturated sodium hydrogen carbonate solution(pH=8.0) and extract with ethyl acetate. Combine the organic phases,wash with water and saturated sodium chloride solution, dry over MgSO₄,filter and evaporate to dryness. Crystallize the resulting solid fromethyl acetate.

[0099] 1d) General Method for the Nitration of the Compounds of Formula(I) or (Ia)

[0100] Add the compound of formula (I) or (Ia) portionwise to ice-cooledconcentrated sulfuric acid without exceeding a reaction temperature of10° C. To the resulting solution add dropwise the nitrating acid (100%HNO₃ dissolved in 95% H₂SO₄) while keeping the reaction temperature alsobelow 10° C. Allow the reaction mixture to agitate 3 hours at 5° C.,then pour it onto ice and render the aqueous phase alkaline with sodiumhydroxide solution. Wash the resulting solid with water and thendissolve it in tert.butyl methyl ether. Wash the organic phase withwater, dry it over Na₂SO₄, filter and evaporate to dryness. Crystallizethe crude product from hexane/methylene chloride or dissolve it in hotacetonitrile and a small amount of 3-molar hydrochloric acid (inethanol) and precipitate the product with water.

[0101] 1e) General Method for the Reduction of the Nitro Compounds tothe Corresponding Arylamines Followed by N-Acetylation

[0102] Reduction of the Arylic Nitro Group

[0103] Dissolve the nitro compound prepared under 1d) in 32% aqueoushydrochloric acid and to the solution add SnCl₂.2H₂O. Heat the reactionmixture at reflux for 1 to 3 hours, then cool to 25° C. Pour thereaction solution onto ice, render the reaction solution alkaline with4-molar sodium hydroxide solution and extract it with tert.butyl methylether. Dry the combined organic phases over Na₂SO₄, filter, acidify witha 3-molar hydrochloric acid solution (in ethanol) and evaporate todryness under reduced pressure. Dissolve the residue in a small amountof 3-molar hydrochloric acid (in ethanol) and add the solution to coldtert.butyl methyl ether. Isolate the precipitated product by filtrationunder nitrogen.

[0104] N-Acetylation

[0105] Dissolve the aforesaid product in acetic acid and add aceticanhydride to the solution. Allow the reaction mixture to agitatevigorously at 25° C. for 1 to 3 hours, then add it to tert.butyl methylether. Collect the resulting precipitate by suction filtration, wash itwith ether and dry under vacuum.

Example 1.1 Synthesis of 1,2,3,3,5-Pentamethyl-3H-Indolium Iodide

[0106] This compound was prepared by the general synthesis method 1 a)by adding 3.0 mL of 97% sulfuric acid to a solution of 3.27 g ofp-tolylhydrazine and 2.87 g of isopropyl methyl ketone in 110 mL ofethanol. The resulting oil was purified by bulb-tube vacuum distillation(0.02-0.07 mbar; 100-105° C.).

[0107] Yield (intermediate): 3.18 g of 2,3,3,5-tetramethyl-3H-indole168% of the theoretical). 1.0 g of the intermediate thus obtained wasalkylated with 4.18 g of methyl iodide according to variant 2 under 1b).

[0108] Yield: 1.11 g of 1,2,3,3,5-pentamethyl-3H-indolium iodide (61% ofthe theoretical).

[0109] Melting point: 224-227° C.

[0110]¹H-NMR (CD₃OD): δ=1.59 ppm (s, 6H); 2.50 ppm (s, 3H); 4.03 ppm (s,3H); 4.83 ppm (s, 3H) (s, 3H); 7.45 ppm (dd, ³J=8 Hz, ⁴J=not resolved,1H); 7.59 ppm (d, ⁴J=not resolved, 1H); 7.70 (d, ³J=8 Hz, 1H).

[0111] FAB¹ mass spectrum: M⁺=188.30 (100% rel intensity)

[0112] Elemental analysis: C₁₃H₁₈NI (315.19) % C % H % N Calcd.: 49.545.76 4.74 Found: 49.80 5.77 4.30

Example 1.2 Synthesis of 1,2,3,3,7-Pentamethyl-3H-IndoliumTetrafluoroborate

[0113] This compound was prepared by the general synthesis method la) byadding 3.1 mL of 97% sulfuric acid to a solution of 3.39 g ofp-tolylhydrazine and 3.0 g of isopropyl methyl ketone in 120 mL ofethanol. The resulting oil was purified by bulb-tube vacuum distillation(0.02-0.07 mbar; 100-105° C.).

[0114] Yield (intermediate): 3.0 g of 2,3,3,7-tetramethyl-3H-indole (62%of the theoretical) 0.50 g of the intermediate thus obtained wasalkylated with 0.51 g of trimethyloxonium tetrafluoroborate and 1 mL of1,2-dichloroethane according to variant 4 under 1b).

[0115] Yield; 0.43 g of 1,2,3,3,7-pentamethyl-3H-indoliumtetrafluoroborate (54% of the theoretical) ¹H-NMR D₆-DMSO): δ=1.50 ppm(s, 6H); 2.74 ppm (s, 3H); 2.75 ppm (s, 3H); 4.11 ppm (s, 3H); 7.35 ppm(dd, ³J=7.5 Hz, ⁴J=not resolved, 1H); 7.46 ppm (dd, ³J=7.5 Hz, 1H); 7.60ppm (dd, ³J=7.5 Hz, ⁴J=not resolved, 1H).

[0116] FAB mass spectrum: M⁺=188.3 (100% rel. intensity)

[0117] Elemental analysis: C₁₃H₁₈NBF₄ (275.10) % C % H % N % F Calcd.:56.76 6.60 5.09 27.62 Found 56.52 6.48 5.21 27.57

Example 1.3 Synthesis of 1,2,3,3,6,7-Hexamethyl-3H-IndoliumTetrafluoroborate

[0118] This compound was prepared by the general synthesis method 1a) byadding 3.1 mL of 97% sulfuric acid to a solution of 3.76 g ofdimethylphenylhydrazine and 2.97 g of isopropyl methyl ketone in 120 mLof ethanol. The resulting oil was purified by bulb-tube vacuumdistillation (0.02-0.07 mbar; 100-105° C.).

[0119] Yield (intermediate): 1.90 g of 2,3,3,6,7-pentamethyl-3H-indole(37% of the theoretical).

[0120] 1.0 g of the intermediate thus obtained was alkylated with 0.95 gof trimethyloxonium tetrafluoroborate and 4 mL of 1,2-dichloroethaneaccording to variant 4 under 1b).

[0121] Yield 0.49 g of 1,2,3,3,6,7-hexamethyl-3H-indoliumtetrafluoroborate (32% of the theoretical).

[0122]¹H(D₆-DMSO): δ=1.45 ppm (s, 6H); 2.37 ppm (s, 3H); 2.61 ppm (s,3H); 2.72 ppm (s, 3H); 4.11 pm (s, 3H); 7.40 ppm (d, ³J=8 Hz, 1H); 7.49ppm (d, ³J=8 Hz, 1H).

[0123] FAB mass spectrum: M⁺=202.3 (100% rel intensity)

[0124] Elemental analysis: C₁₄H₂₀NBF₄ (289.121) % C % H % N % F Calcd.:58.16 6.97 4.84 26.28 Found 57.86 6.88 4.78 26.15

Example 1.4 Synthesis of 1,2,3,3,5,7-Hexamethyl-3H-IndoliumTetrafluoroborate

[0125] This compound was prepared by the general synthesis method 1a) byadding 3.2 mL of 97% sulfuric acid to a solution of 4.57 g ofdimethylphenylhydrazine and 3.08 g of isopropyl methyl ketone in 80 mLof ethanol. The resulting oil was purified by bulb-tube vacuumdistillation (0.02-0.07 mbar; 100-105° C/).

[0126] Yield (intermediate): 2.67 g of 2,3,3,5,7-pentamethyl-3H-indole(50% of the theoretical).

[0127] 1.0 g of the intermediate thus obtained was alkylated with 0.95 gof trimethyloxonium tetrafluoroborate and 4 mL of 1,2-dichloroethaneaccording to variant 4 under 1b).

[0128] Yield 0.79 g of 1,2,3,3,5,7-hexamethyl-3H-indoliumtetrafluoroborate (51% of the theoretical).

[0129]¹H-NMR (D₆-DMSO): δ=1.45 ppm (s, 6H); 2.36 ppm (s, 3H); 2.69 ppm(s, 3H); 2.70 ppm (s, 3H); 4.07 ppm (s, 3H); 7.18 ppm (s, 1H); 7.44 ppm(s, 1H).

[0130] FAB mass spectrum: M⁺=202.3 (100% rel intensity)

[0131] Elemental analysis: C₁₄H₂₀NBF₄ (289.12) % C % H % N % F Calcd.:58.16 6.97 4.84 26.28 Found 57.94 6.86 4.81 26.32

Example 1.5 Synthesis of 1,2,3,3,4,7-Hexamethyl-3H-IndoliumTetrafluoroborate

[0132] This compound was prepared by the general synthesis method 1a) byadding 3.1 mL of 97% sulfuric acid to a solution of 3.70 g ofdimethylphenylhydrazine and 2.93 g of isopropyl methyl ketone in 80 mLof ethanol. The resulting oil was purified by bulb-tube vacuumdistillation (0.02-0.07 mbar; 100-105° C.).

[0133] Yield (intermediate): 3.58 g of 2,3,3,4,7-pentamethyl-3H-indole(70% of the theoretical).

[0134] 1.0 g of the intermediate thus obtained was alkylated with 0.95 gof trimethyloxonium tetrafluoroborate and 4 mL of 1,2-dichloroethaneaccording to variant 4 under 1b).

[0135] Yield; 0.83 g of 1,2,3,3,4,7-hexamethyl-3H-indoliumtetrafluoroborate (53% of the theoretical).

[0136]¹H-NMR D₆-DMSO): δ=1.53 ppm (s, 6H); 2.47 ppm (s, 3H); 2.70 ppm(s, 3H); 2.72 ppm (s, 3H); 4.07 ppm (s, 3H); 7.23 ppm (d, ³J=8 Hz, 1H);7.27 ppm (d, ³J=8 Hz, 1H).

[0137] FAB mass spectrum: M⁺=202.3 (100% rel intensity)

[0138] Elemental analysis: C₁₄H₂₀NBF₄ (289.12) % C % H % N % F Calcd.:58.16 6.97 4.84 26.28 Found 58.10 6.86 4.80 26.11

Example 1.6 Synthesis of 5-Methoxy-1,2,3,3-Tetramethyl-3H-IndoliumIodide

[0139] This compound was prepared by the general synthesis method 1a) byadding 8.0 g of 4-methoxyphenylhydrazine and 6.23 g of isopropyl methylketone to 120 mL of ethanol and 11.3 g of 97% sulfuric acid. Theresulting oil was purified by bulb-tube vacuum distillation (0.02-0.07mbar; 100-105° C.).

[0140] Yield (intermediate): 6.34 g of5-methoxy-2,3,3,-trimethyl-3H-indole (58% of the theoretical).

[0141] 1.0 g of the intermediate thus obtained was alkylated with 1.59 gof methyl iodide and 7.2 mL of chloroform according to variant 1 under1b).

[0142] Yield: 1.11 g of 1,2,3,3,5-pentamethyl-3H-indolium iodide (58% ofthe theoretical).

[0143]¹H-NMR (CD₃OD): δ=1.59 ppm (s, 6H); 3.91 ppm (s, 3H); 4.02 ppm (s,3H); 4.85 ppm (s, 3H); 7.15 ppm (dd, ³J=9 Hz, ⁴J=2 Hz, 1H); 7.35 ppm (d,⁴J=2 Hz, 1H); 7.73 ppm (d, ³J=9 Hz, 1H ).

[0144] FAB mass spectrum: M⁺=204.0 (100% rel. intensity), 188 (44% rel.intensity)

[0145] Elemental analysis: C₁₃H₁₈NOI (331.20) % C % H % N % O Calcd.:47.15 5.48 4.23 4.83 Found 47.30 6.10 4.30 4.90

Example 1.7 Synthesis of 5-Fluoro-1,2,3,3-Tetramethyl-3H-Indolium Iodide

[0146] This compound was prepared by the general synthesis method 1 a)by adding 3.0 g of 4-fluorophenyl-hydrazine and 2.48 g of isopropylmethyl ketone to 65 mL of ethanol and 2.6 mL of 97% sulfuric acid. Theresulting solid was melted and purified by bulb-tube vacuum distillation(0.02-0.07 mbar; 100-105° C.).

[0147] Yield (intermediate): 3.21 g of5-fluoro-2,3,3-trimethyl-3H-indole (76% of the theoretical).

[0148] 1.0 g of the intermediate thus obtained was alkylated with 0.91 gof methyl iodide and 3 mL of chloroform according to variant 1 under1b).

[0149] Yield: 0.70 g (39% of the theoretical).

[0150]¹H-NMR (CD₃OD): δ=1.62 ppm (s, 6H); 4.06 ppm (s, 3H); 4.85 ppm (s,3H); 7.38-7.42 ppm (m, 1H); 7.61-7.63 ppm (m, 1H); 7.86-7.89 ppm (m,1H).

[0151] FAB mass spectrum: M⁺=192.20 (100% rel. intensity)

[0152] Elemental analysis: C₁₂H₁₅NFI (319.16) % C % H % N % F Calcd.:45.16 4.74 4.39 5.95 Found 44.70 4.90 4.30 6.00

Example 1.8 Synthesis of 5-Isopropyl-1,2,3,3-Tetramethyl-3H-IndoliumIodide

[0153] This compound was prepared by the general synthesis method 1a) byadding 3.71 g of 4-isopropyl-phenylhydrazine and 2.66 g of isopropylmethyl ketone to 90 mL of ethanol and 2.9 mL of 97% sulfuric acid. Theresulting oil was purified by bulb-tube vacuum distillation (0.02-0.07mbar; 100-105° C).

[0154] Yield (intermediate): 4.11 g of5-isopropyl-2,3,3-trimethyl-3H-indole (83% of the theoretical).

[0155] 1.0 g of the intermediate thus obtained was alkylated with 0.81 gof methyl iodide and 3 mL of chloroform according to variant 1 under1b).

[0156] Yield: 0.63 g of 5-isopropyl-1,2,3,3-tetramethyl-3H-indoliumiodide (37% of the theoretical).

[0157]¹H-NMR (CD₃OD): δ=1.31 ppm (d, ³J=7 Hz, 6H); 1.60 ppm (s, 6H);3.06-3.12 (m, 1H); 4.04 ppm (s, 3H); 4.84 ppm (s, 3H); 7.52 ppm (dd,³J=9 Hz, ⁴J 2 Hz, 1H); 7.66 ppm (d, ⁴J=2 Hz, 1H); 7.73 ppm (d, ³J=8 Hz,1H).

[0158] FAB mass spectrum: M⁺216.3 (100% rel. intensity)

[0159] Elemental analysis: C₁₆H₂₂NI (343.31) % C % H % N Calcd.: 52.486.46 4.08 Found 52.90 6.80 3.82

Example 1.9 Synthesis of 5-Hydroxy-1,2,3,3-Tetramethyl-3H-IndoliumIodide

[0160] This compound was prepared by the general synthesis method 1c)from 4.0 g of 5-methoxy-2,3,3-trimethyl-3H-indole, 16 mL of acetic acidand 16 mL of 48% hydrobromic acid solution.

[0161] Yield (intermediate): 2.45 g of5-hydroxy-2,3,3-trimethyl-3H-indole (66% of the theoretical).

[0162] 1.0 g of the intermediate thus obtained was alkylated with 1.66 gof methyl iodide and 10 mL of methanol according to variant 3 under 1b).

[0163] Yield: 1.36 g of 5-hydroxy-1,2,3,3-tetramethyl-3H-indolium iodide(75% of the theoretical).

[0164] Melting point: 245-247° C.

[0165]¹H-NMR (D₆-DMSO): δ=1.46 ppm (s, 6H); 2.66 ppm (s, 3H); 3.89 ppm(s, 3H); 6.93 ppm (dd, ³J=9 Hz, ⁴J=2 Hz, 1H); 7.11 ppm (d, ⁴J=2 Hz, 1H);7.67 ppm (d, ³J=9 Hz, 1H); 10.22 ppm (s, exchanges with D₂O, 1H).

[0166] FAB mass spectrum: M⁺=190.10 (100% rel. intensity)

[0167] Elemental analysis: C₁₂H₁₆NOI (317.17) % C % H % N % O Calcd.:45.44 5.08 4.42 5.04 Found 45.50 5.60 4.40 5.60

Example 1.10 Synthesis of 5-Nitro-1,3,3-Trimethyl-2-Methyleneindoline

[0168] This compound was prepared by the general synthesis method 1d)from a solution of 20 g of 1,3,3-trimethyl-2-methyleneindoline in 50 mLof 97% sulfuric acid and 23.5 mL of nitrating acid (a mixture of 3.5 mLof fuming 99% nitric acid and 20 mL of 97% sulfuric acid). The crudeproduct was crystallized from hexane/methylene chloride.

[0169] Yield: 8.8 g of 5-nitro-1,3,3-trimethyl-2-methyleneindoline (35%of the theoretical).

[0170] Melting point: 89-91° C.

[0171]¹H-NMR (CDCl₃): δ=1.35 ppm (s, 6H); 3.11 ppm (s,3H); 4.09 ppm (d,²J=3 Hz, 1H); 4.11 ppm (d, ²J=2.5 Hz, 1H); 6.51 ppm (d, ³J=9 Hz, 1H);7.91 ppm (d, ⁴J=2.5 Hz, 1H); 8.11 ppm (dd, ²J=9 Hz, ⁴J=2.5 Hz, 1H);

[0172] El mass spectrum: 218 (85, M⁺); 203 (100); 188 (6); 171 (16); 157(91); 145 (32); 1.45 (32); 1.28 (24); 115 (44); 103 (10); 89 (15); 77(14); 63 (12).

Example 1.11 Synthesis of5-Methoxy-6-Nitro-1,2,3,3-Tetramethyl-3H-Indolium Chloride

[0173] This compound was prepared by the general synthesis method 1d)from a solution of 0.50 g of 5-methoxy-1,2,3,3-tetramethyl-3H-indoliumiodide in 5 mL of 97% sulfuric acid and using 0.5 ml of nitrating acid(mixture consisting of 1.5 mL of fuming 99% nitric acid and 10 mL of 97%sulfuric acid). The crude product was dissolved in about 2 mL of hotacetonitrile with the aid of 3 M hydrochloric acid in ethanol (about 0.5mL). Addition of water caused the pure product to precipitate.

[0174] Yield: 0.22 g of5-methoxy-6-nitro-1,2,3,3-tetramethyl-3H-indolium chloride (45% of thetheoretical).

[0175]¹H-NMR (D₆-DMSO): δ=1.58 ppm (s, 6H); 2.78 ppm (s, 3H); 3.98 ppm(s, 3H); 4.05 ppm (s, 3H); 8.05 ppm (s, 1H); 8.60 ppm (s, 1H)

[0176]¹³C-NMR (D₆DMSO) δ=14.4 ppm (q); 21.5 ppm (q); 35.2 ppm (q); 54.7ppm (s); 57.9 ppm (q); 110.2 ppm (d); 112.3 ppm (d); 134.5 ppm (s);139.0 ppm (s); 147.4 ppm (s); 153.1 ppm (s); 196.2 ppm (s).

[0177] FAB mass spectrum: M⁺249.2 (100% rel. intensity)

[0178] Elemental analysis: C₁₃H₁₇N₂O₃Cl (284.74) % C % H % N % O Calcd.:54.84 6.02 9.84 16.86 Found 54.30 5.80 9.70 17.40

Example 1.12 Synthesis of5-N-Acetylamino-1,2,3,3-Tetramethyl-3H-Indolium Acetate

[0179] This compound was prepared by the general synthesis method 1e)and using for the reaction 1.3 g of5-nitro-1,3,3-trimethyl-2-methyleneindoline, 39 mL of 32% hydrochloricacid and 8.10 g of SnCl₂. 2 H₂O. The N-acetylation reaction was carriedout with 1.48 g of 5-amino-1,2,3,3-tetramethyl-3H-indolium chloride, 37mL of acetic acid and 37 mL of acetic anhydride.

[0180] Yield: 1.41 g of 5-N-acetylamino-1,2,3,3-tetramethyl-3H-indoliumacetate (82% of the theoretical).

[0181]¹H-NMR (D₆-DMSO): δ=1.48 ppm (s, 6H); 1.90 ppm (s, 3H from AcO⁻);2.09 ppm (s, 3H); 2.71 ppm (s, 3H); 3.93 ppm (s, 3H); 7.74 ppm (dd, ³J=9Hz, ⁴J=2 Hz, 1H); 7.83 ppm (d, ³J=9 Hz, 1H); 8.08 ppm (d, ⁴J=2 Hz, 1H);10.73 ppm (s, 1H).

[0182] El mass spectrum: 230 (67, M⁺); 215 (100); 199 (5); 187 (10); 173(25); 145 (35); 130 (10); 115 (6); 103 (5); 77 (8).

Example 1.13 Synthesis of1,2-Dimethyl-5-Methoxy-3-(Spirocyclohexyl)-3H-Indolium Tetrafluoroborate

[0183] This compound was prepared by the general synthesis method la)from 3.0 g of 4-methoxyphenyl-hydrazine, 3.42 g of cyclohexyl methylketone in 50 mL of ethanol and 4.43 g of 97% sulfuric acid. Theresulting oil was purified by chromatography (silica gel;hexane:EtOAc=6:4). This gave 1.46 g of5-methoxy-2-methyl-3-(spirocyclohexyl)-3H-indole (29% of thetheoretical).

[0184] 1.11 of the intermediate thus obtained was alkylated with 3.10 gof trimethyloxonium tetrafluoroborate (4.3 equivalents) and 20 mL of1,2-dichloroethane according to synthesis method 1b) (variant 4).

[0185] Yield: 1.26 g of1,2-dimethyl-5-methoxy-3-(spirocyclohexyl)-3H-indolium tetrafluoroborate(79% of the theoretical).

[0186]¹H-NMR (D₆DMSO): δ=1.33-1.60 ppm (m, 3H); 1.70-2.10 ppm (m, 7H);2.71 ppm (s, 3H); 3.88 ppm (s, 3H); 3.92 ppm (s, 3H); 7.21 ppm (dd, ³J=9Hz, ⁴J=2.0 Hz, 1H); 7.51 ppm (d, ⁴J=2.0 Hz, 1H); 7.86 ppm (d, ³J=9.0 Hz,1H).

[0187] FAB mass spectrum: M⁺=244.2 (100% rel. intensity) Elementalanalysis: C₁₆H₂₂NOBF₄ (331.16) % C % H % N % F % O Calcd.: 58.03 6.704.23 22.95 4.83 Found 57.70 6.80 4.20 23.00 4.80

Examples 2.1 to 5.5 Hair Coloring Solution

[0188] Indole-Containing Component A1 Quantities shown Indole derivativeof formula (I)/(Ia) in Tables 1-4 Lauryl ether sulfate (28% aqueoussolution) 1 g Ethanol 2 g Water, demineralized to 10 g

[0189] The pH of the solution was adjusted to the value indicated inTables 1 to 4 with 20% aqueous monoethanolamine solution.Aldehyde-Containing Component A2 Quantities shown Aldehyde compound inTables 1-4 Lauryl ether sulfate (28% aqueous solution) 1 g Ethanol 2 gWater, demineralized to 10 g

[0190] The pH of component A2 was between 4 and 5.

[0191]1 g of component A1 was mixed with 1 g of component A2. Theresulting pH, (pH of the mixture of components A1+A2) is given in Tables1 to 4.

[0192] The resulting ready-for-use hair colorant was applied to bleachedhair and uniformly distributed with a brush. After an exposure time of30 min at 40° C., the hair was washed with a shampoo, rinsed withluke-warm water and then dried.

[0193] The hair can be completely decolorized at any point in time (forexample after several days or weeks) within 20 min at 40° C. with anacidic (pH=5) 5% sodium sulfite solution.

[0194] The results of the coloring and decolorizing are summarized inthe following Tables 1 to 4. TABLE 1 Coloring Results A1)Indole-containing component, pH 8.8 A2) Aldehyde-containing Shade AfterColor-Measuring Values No. component Coloring L a b 2.1 A1)1,2,3,3,5-pentamethyl- purple untreated hair +83.30  −0.48 +10.403H-indolium iodide, 0.30 g, after dyeing +39.01 +36.77  +0.13 A2)3,5-dimethoxy-4-hy- droxybenzaldehyde, 0.17 g, pH_(m): 8.1 2.2 A1)1,2,3,3,5-pentamethyl- intense untreated hair +83.30  −0.48 +10.403H-indolium iodide, 0.30 g orange after dyeing +51.07   43.03 +23.06 A2)4-hydroxy-3-methoxy- benzaldehyde, 0.15 g, pH_(m): 7.9 2.3 A1)1,2,3,3,5-pentamethyl- intense untreated hair +83.30  −0.48 +10.403H-indolium iodide, 0.30 g yellow after dyeing +75.13 +12.17 +73.24 A2)3-hydroxy-4-methoxy- benzaldehyde, 0.15 g pH_(m): 8.7 2.4 A1)1,2,3,3,5-pentamethyl- intense untreated hair +83.30  −0.48 +10.403H-indolium iodide, 0.30 g wine-red after dyeing +30.54 +28.38  +1.58 A23,4,5-trihydroxy- benzaldehyde, 0.16 g, pH_(m): 7.8 2.5 A1)1,2,3,3,5-pentamethyl- intense untreated hair +83.30  −0.48 +10.40indolium iodide, 0.30 g pink after dyeing +52.58 +61.46  +4.29 A2)4-(dimethylamino)- benzaldehyde, 0.14 g pH_(m): 8.8

[0195] TABLE 2 Coloring Results A1) Indole-containing component, pH 8.2Shade After A2) Aldehyde-containing Coloring/ Color-Measuring Values No.component Decolorizing L a b 3.1 A1) 5-isopropyl-1,2,3,3-tetra- purpleuntreated hair +83.30  −0.48 +10.40 methyl-3H-indolium iodide, 0.33 gafter dyeing +36.29 +40.00  −1.35 A2) 3,5-dimethoxy-4-hydroxy- afterdecolo- white benzaldehyde, 0.17 g rizing pH_(m): 7.7 3.2 A1)5-isopropyi-1,2,3,3-tetra- intense untreated hair +83.30  −0.48 +10.40methyl-3H-indolium iodide, 0.33 g orange after dyeing +48.10 +49.18+25.14 A2) 4-hydroxy-3-methoxy after decolo- white benzaldehyde, 0.15 grizing pH_(m): 7.7 3.3 A1) 5-isopropyl-1,2,3,3-tetra- intense untreatedhair +83.30  −0.48 +10.40 methyl-3H-indolium iodide, 0.33 g yellow afterdyeing +75.70 +11.98 +64.39 A2) 3-hydroxy-4-methoxy-benz- after decolo-white aldehyde, 0.15 g rizing pH_(m): 8.3 3.4 A1)5-isopropyl-1,2,3,3-tetra- intense untreated hair +83.30  −0.48 +10.40methyl-3H-indolium iodide, 0.33 g eggplant after dyeing +40.79 +15.34 +0.69 A2) 3,4,5-trihydroxybenzaldehyde, after decolo- white 0.16 grizing pH_(m): 7.6 3.5 A1) 5-isopropyl-1,2,3,3-tetra- intense untreatedhair +83.30  −0.48 +10.40 methyl-3H-indolium iodide, 0.33 g pink afterdyeing +57.30 +56.83  +1.75 A2) 4-(dimethylamino)benzaldehyde afterdecolo- white 0.14 g rizing pH_(m: 8.4)

[0196] TABLE 3 Coloring Results A1) Indole-containing component, pH 8.5Shade After A2) Aldehyde-containing Coloring/ Color-Measuring Values No.component Decolorizing L a b 4.1 A1) 5-fluoro-1,2,3,3-tetramethyl-eggplant untreated hair +83.30  −0.48 +10.40 3H-indolium iodide, 0.30 gafter dyeing +35.91 +44.47 −11.23 A2) 3,5-dimethoxy-4-hydroxy- afterdecolo- white benzaldehyde, 0.17 g rizing pH_(m): 7.8 4.2 A1)5-fluoro-1,2,3,3-tetramethyl- red untreated hair +83.30  −0.48 +10.403H-indolium iodide, 0.30 g after dyeing +40.79 +59.23 +20.40 A2)4-hydroxy-3-methoxybenz- after decolo- white aldehyde, 0.15 g rizingpH_(m): 7.9 4.3 A1) 5-fluoro-1,2,3,3-tetramethyl- intense untreated hair+83.30  −0.48 +10.40 3H-indolium iodide, 0.30 g yellow after dyeing+72.32 +17.57 +77.71 A2) 3-hydroxy-4-methoxy- after decolo- whitebenzaldehyde, 0.15 g rizing pH_(m): 8.5 4.4 A1)5-fluoro-1,2,3,3-tetramethyl- eggplant untreated hair +83.30  −0.48+10.40 3H-indolium iodide, 0.30 g after dyeing +29.44 +27.82 −10.86 A2)3,4,5-trihydroxybenz- after decolo- white aldehyde, 0.16 g rizingpH_(m): 7.8 4.5 A1) 5-fluoro-1,2,3,3-tetramethyl- intense untreated hair+83.30  −0.48 +10.40 3H-indolium iodide, 0.30 g pink after dyeing +58.58+55.54  +1.32 A2) 4-(dimethylamino)benz- after decolo- light-pinkaldehyde, 0.14 g rizing pH_(m): 8.5

[0197] TABLE 4 Coloring Results A1) Indole-containing component, pH 9.4A2) Aldehyde-containing Shade After Color-Measuring Values No. componentColoring L a b 5.1 A1) 5-methoxy-1,2,3,3-tetramethyl- wine-red untreatedhair +83.30  −0.48 +10.40 3H-indolium iodide, 0.32 g after dyeing +23.77+42.40  +7.96 A2) 3,5-dimethoxy-4-hydroxy- benzaldehyde, 0.17 g pH_(m):8.3 5.2 A1) 5-methoxy-1,2,3,3-tetramethyl- red untreated hair +83.30 −0.48 +10.40 3H-indolium iodide, 0.32 g after dyeing +36.46 +55.82+31.27 A2) 4-hydroxy-3-methoxybenz- aldehyde, 0.15 g pH_(m): 8.2 5.3 A1)5-methoxy-1,2,3,3-tetramethyl- orange untreated hair +83.30  −0.48+10.40 3H-indolium iodide, 0.32 g after dyeing +62.18 +35.08 +76.67 A2)3-hydroxy-4-methoxy- benzaldehyde, 0.15 g pH_(m): 8.6 5.4 A1)5-methoxy-1,2,3,3-tetramethyl- intense untreated hair +83.30  −0.48+10.40 3H-indolium iodide, 0.32 g wine-red after dyeing +20.57 +31.59 +6.62 A2) 3,4,5-trihydroxybenz- aldehyde, 0.16 g pH_(m): 7.9 5.5 A1)5-methoxy-1,2,3,3-tetramethyl- intense untreated hair +83.30  −0.48+10.40 3H-indolium iodide, 0.32 g pink after dyeing +38.52 +64.34  +4.33A2) 4-(dimethylamino)- benzaldehyde, 0.14 g pH_(m): 8.7

Coloring Examples 6.1 to 12.5 Hair Colorants in Cream Form

[0198] Component A1 with Indole Derivative Quantities shown Indolederivative of formula (I)/(Ia) in Tables 5-11 Cetylstearyl alcohol 12 gLauryl ether sulfate, 28% aqueous solution 10 g Ethanol 23 g Water,demineralized to 100 g

[0199] The cetylstearyl alcohol was melted at 80° C. The lauryl ethersulfate and 95% of the water were heated to 80° C., added to the moltencetylstearyl alcohol and stirred until a cream formed. Compound (I)/(Ia)mixed with the ethanol and the remainder of the water were added at roomtemperature. The pH of the cream was adjusted to the value given inTables 5 to 10 with 20% aqueous monoethanolamine solution. AldehydeComponent A2 Quantities shown Aldehyde compound in Tables 5-11Cetylstearyl alcohol 12 g Lauryl ether sulfate, 28% aqueous solution 10g Ethanol 23 g Water, demineralized to 100 g

[0200] The cetylstearyl alcohol was melted at 80° C. The lauryl othersulfate and 95% of the water were heated to 80° C., added to the moltencetylstearyl alcohol and stirred until a cream formed. The aldehydemixed with the ethanol and the remainder of the water were added at roomtemperature. The pH of component A2 was between 4 and 5.

[0201] Components A1 and A2 were mixed in a 1:1 ratio. The measured pHof the mixture is indicated in Tables 5 to 11 as pH_(m). Theready-for-use hair colorant obtained in this manner was applied tobleached hair and uniformly distributed with a brush. After an exposuretime of 30 min at 40° C., the hair was washed with a shampoo, rinsedwith luke-warm water and then dried.

[0202] The hair can be completely decolorized at any point in time (forexample after several days or weeks) within 20 min at 40° C. with anacidic (pH=5) 5% sodium sulfite solution.

[0203] The results of the coloring and decolorizing are summarized inthe following Tables 5 to 11. TABLE 5 Coloring Results A1)Indole-containing component, pH 7.6 Shade After A2) Aldehyde-containingColoring/ Color-Measuring Values No. component Decolorizing L a b 6.1A1) 1,2,3,3,5-pentamethyl- purple untreated hair +83.30  −0.48 +10.403H-indolium iodide, 3.62 g after dyeing +21.23 +42.37  +2.40 A2)3,5-dimethoxy-4-hydroxy- after decolo- white benzaldehyde, 2.09 g rizingpH_(m): 7.6 6.2 A1) 1,2,3,3,5-pentamethyl- red untreated hair +83.30 −0.48 +10.40 3H-indolium iodide, 3.62 g after dyeing +31.41 +57.08+22.71 A2) 4-hydroxy-3-methoxy- after decolo- white benzaldehyde, 1.75 grizing pH_(m): 7.4 6.3 A1) 1,2,3,3,5-pentamethyl- intense untreated hair+83.30 −0.48 +10.40 3H-indolium iodide, 3.62 g yellow after dyeing+61.71 +31.44 +73.16 A2) 3-hydroxy-4-methoxy- after decolo- whitebenzaldehyde, 1.75 g rizing pH_(m): 8.1 6.4 A1) 1,2,3,3,5-pentamethyl-intense untreated hair +83.30  −0.48 +10.40 3H-indolium iodide, 3.62 gwine-red after dyeing +18.17 +17.64  +0.50 A2) 3,4,5-trihydroxy- afterdecolo- white benzaldehyde, 1.98 g rizing pH_(m): 7.6 6.5 A1)1,2,3,3,5-pentamethyl- intense untreated hair +83.30  −0.48 +10.403H-indolium iodide, 3.62 g pink after dyeing +41.53 +66.93  +7.15 A2)4-(dimethylamino)- after decolo- light-pink benzaldehyde, 1.72 g rizingpH_(m): 8.1

[0204] TABLE 6 Coloring Results A1) Indole-containing component, pH 8.6A2) Aldehyde-containing Shade After Color Measuring Values No. componentColoring/Decolorizing L a b 7.1 A1) 1,2,3,3,5,7-hexamethyl-3H- purpleuntreated hair +83.30  −0.48 +10.40 indolium tetrafluoraborate, 3.33 gafter dyeing +31.90 +40.52 −2.37 A2) 3,5-dimethoxy-4-hydroxy- afterdecolorizing white benzaldehyde, 2.09 g pH_(m): 7.4 7.2 A1)1,2,3,3,5,7-hexamethyl-3H- red untreated hair +83.30  −0.48 +10.40indolium tetrafluoroborate, 3.33 g after dyeing +41.40 +53.50 +19.41 A2)4-hydroxy-3-methoxy- after decolorizing white benzaldehyde, 1.75 gpH_(m): 7.3 7.3 A1) 1,2,3,3,5,7-hexamethyl-3H- yellow untreated hair+83.30 −0.48 +10.40 indolium tetrafluoroborate, 3.33 g after dyeing+71.97 +16.17 +70.08 A2) 3-hydroxy-4-methoxy- after decolorizing whitebenzaldehyde, 1.75 g pH_(m): 8.2 7.4 A1) 1,2,3,3,5,7-hexamethyl-3H-intense untreated hair +83.30  −0.48 +10.40 indolium tetrafluoroborate,3.33 g wine-red after dyeing +24.12 +24.20  +0.40 A2)3,4,5-trihydroxybenzaldehyde after decolorizing greenish 1.98 g pH_(m):7.1 7.5 A1) 1,2,3,3,5,7-hexamethyl-3H- intense untreated hair +83.30−0.48 +10.40 indolium tetrafluoroborate, 3.33 g pink after dyeing +54.09+56.26  +3.81 A2) 4-(dimethylamino)benz- after decolorizing pinkishaldehyde, 1.72 g pH_(m): 8.3

[0205] TABLE 7 Coloring Results A1) Indole-containing component, pH 8.6A2) Aldehyde-containing Shade After Color Measuring Values No. componentColoring/Decolorizing L a b 8.1 A1) 1,2,3,3,4,7-hexamethyl-3H- wine-reduntreated hair +83.30  −0.48 +10.40 indolium tetrafluoroborate, 3.33 gafter dyeing +38.72 +36.18  −2.74 A2) 3,5-dimethoxy-4-hydroxy- afterdecolorizing white benzaldehyde, 2.09 g pH_(m): 7.4 8.2 A1)1,2,3,3,4,7-hexamethyl-3H- red untreated hair +83.30  −0.48 +10.40indolium tetrafluoroborate, 3.33 g after dyeing +47.44 +47.58 +13.40 A2)4-hydroxy-3-methoxy- after decolorizing white benzaldehyde, 1.75 gpH_(m): 7.3 8.3 A1) 1,2,3,3,4,7-hexamethyl-3H- yellow untreated hair+83.30  −0.48 +10.40 indolium tetrafluoroborate, 3.33 g after dyeing+76.06  +5.77 +59.77 A2) 3-hydroxy-4-methoxy- after decolorizing whitebenzaldehyde, 1.75 g pH_(m): 8.4 8.4 A1) 1,2,3,3,4,7-hexamethyl-3H-intense untreated hair +83.30  −0.48 +10.40 indolium tetrafluoroborate,3.33 g wine-red after dyeing +30.30 +23.21  +1.08 A2)3,4,5-trihydroxybenzaldehyde after decolorizing yellowish 1.98 g pH_(m):7.2 8.5 A1) 1,2,3,3,4,7-hexamethyl-3H- intense untreated hair +83.30 −0.48 +10.40 indolium tetrafluoroborate, 3.33 g pink after dyeing+63.61 +47.19  +7.90 A2) 4-(dimethylamino) after decolorizing pinkishbenzaldehyde, 1.72 g pH_(m): 8.4

[0206] TABLE 8 Coloring Results A1) Indole-containing component, pH 8.6A2) Aldehyde-containing Shade After Color Measuring Values No. componentColoring/Decolorizing L a b 9.1 A1) 5-methoxy-1,2,3,3,-tetra- wine-reduntreated hair +83.30  −0.48 +10.40 methyl-3H-indolium iodide, 3.83 gafter dyeing +22.27 +39.15  +2.34 A2) 3,5-dimethoxy-4-hydroxy- afterdecolo- white benzaldehyde, 2.09 g rizing pH_(m): 7.8 9.2 A1)5-methoxy-1,2,3,3-tetra- untreated hair +83.30  −0.48 +10.40methyl-3H-indolium iodide, 3.83 g after dyeing +32.44 +56.47 +22.50 A2)4-hydroxy-3-methoxy- white benzaldehyde, 1.75 g pH_(m): 7.6 9.3 A1)5-methoxy-1,2,3,3,tetra- orange untreated hair +83.30  −0.48 +10.40methyl-3H-indolium iodide, 3.83 g after dyeing +64.11 +30.84 +74.52 A2)3-hydroxy-4-methoxy after decolorizing white benzaldehyde, 1.75 gpH_(m): 8.7 9.4 A1) 5-methoxy-1,2,3,3-tetra- intense untreated hair+83.30  −0.48 +10.40 methyl-3H-indolium iodide, 3.83 g wine-red afterdyeing +19.45 +21.11  +1.23 A2) 3,4,5-trihydroxybenzaldehyde afterdecolorizing white 1.98 g pH_(m): 7.5 9.5 A1) 5-methoxy-1,2,3,3,-tetra-intense untreated hair +83.30  −0.48 +10.40 methyl-3H-indolium iodide,3.83 g pink after dyeing +48.28 +61.52  +0.08 A2) 4-(dimethylaminobenz-after decolorizing white aldehyde, 1.75 g pH_(m): 8.2

[0207] TABLE 9 Coloring Results A1) Indole-containing component, pH 8.4Shade After A2) Aldehyde-containing Coloring/ Color-Measuring Values No.component Decolorizing L a b 10.1 A1) 5-hydroxy-1,2,3,3,-tetra- wine-reduntreated hair +83.30  −0.48 +10.40 methyl-3H-indolium iodide, 3.65 gafter dyeing +26.90 +32.82  +4.88 A2) 3,5-dimethoxy-4-hydroxy- afterdecolorizing white benzaldehyde, 2.09 g pH_(m): 7.3 10.2 A1)5-hydroxy-1,2,3,3-tetra- red untreated hair +83.30  −0.48 +10.40methyl-3H-indolium iodide, 3.65 g after dyeing +36.67 +47.42 +24.17 A2)4-hydroxy-3-methoxy- after decolorizing white benzaldehyde, 1.75 gpH_(m): 7.3 10.3 A1) 5-hydroxy-1,2,3,3,-tetra- orange untreated hair+83.30  −0.48 +10.40 methyl-3H-indolium iodide, 3.65 g after dyeing+58.89 +23.29 +63.05 A2) 3-hydroxy-4-methoxy- after decolorizing whitebenzaldehyde, 1.75 g pH_(m): 8.0 10.4 A1) 5-hydroxy-1,2,3,3-tetra-intense untreated hair +83.30  −0.48 +10.40 methyl-3H-indolium iodide,3.65 g wine-red after dyeing +24.66 +24.35  +4.62 A2) 3,4,5-trihydroxy-after decolorizing white benzaldehyde, 1.98 g pH_(m): 7.1 10.5 A1)5-hydroxy-1,2,3,3,-tetra- intense untreated hair +83.30  −0.48 +10.40methyl-3H-indolium iodide, 3.65 g pink after dyeing +46.09 +42.68  −2.65A2) 4-(dimethylamino)benzal- after decolorizing bright-pink dehyde, 1.72g pH_(m): 8.1

[0208] TABLE 10 Coloring Results A1) Indole-containing component, pH 8.4Shade After A2) Aldehyde-containing Coloring/ Color-Measuring Values No.component Decolorizing L a b 11.1 A1) 5-hydroxy-1,2,3,3,-tetra- intenseuntreated hair +83.30  −0.48 +10.40 methyl-3H-indolium iodide, 3.65 geggplant after dyeing +22.41 +25.83  −3.60 A2) 3,5-dimethoxy-4-hydroxy-after decolorizing white benzaldehyde, 2.09 g pH_(m): 9.9 11.2 A1)5-hydroxy-1,2,3,3-tetra- red untreated hair +83.30  −0.48 +10.40methyl-3H-indolium iodide, 3.65 g after dyeing +31.07 +40.01 +12.18 A2)4-hydroxy-3-methoxy- after decolorizing white benzaldehyde, 1.75 gpH_(m): 10.0 11.3 A1) 5-hydroxy-1,2,3,3,-tetra- black untreated hair+83.30  −0.48 +10.40 methyl-3H-indolium iodide, 3.65 g after dyeing+17.95  +9.23  −0.30 A2) 3,4,5-trihydroxybenz- after decolorizing whitealdehyde, 1.98 g pH_(m): 9.7 11.4 A1) 5-hydroxy-1,2,3,3-tetra- intenseuntreated hair +83.30  −0.48 +10.40 methyl-3H-indolium iodide, 3.65 gpink after dyeing +29.12 +41.38  −5.46 A2) 4-(dimethylamino)benz- afterdecolorizing bright pink aldehyde, 1.72 g pH_(m): 10.2

[0209] TABLE 11 Coloring Results A1) Indole-containing component, pH 9.2Shade After A2) Aldehyde-containing Coloring/ Color-Measuring Values No.component Decolorizing L a b 12.1 A1 1,2-dimethyl-5-methoxy-3- purpleuntreated hair +83.30  −0.48 +10.40 (spirocyclohexul-3H-indolium afterdyeing +56.75 +10.85  +1.07 tetrafluoroborate, 0.95 g A2)3,5,dimethoxy-4-hydroxy- after decolorizing white benzaldehyde, 0.52 gpH_(m) = 8.4 12.2 A1 1,2-dimethyl-5-methoxy-3- red untreated hair +83.30 −0.48 +10.40 (spirocyclohexyl)-3H-indolium- after dyeing +65.23 +22.28 +9.42 tetrafluoroborate, 0.95 g A2) 4-hydroxy-3-methoxy- afterdecolorizing white benzaldehyde, 0.44 g pH_(m) = 8.4 12.3 A11,2-dimethyl-5-methoxy-3- yellow untreated hair +83.30  −0.48 +10.40(spirocyclohexyl)-3H-indolium after dyeing +79.41  +4.27 +33.94tetrafluoroborate, 0.95 g A2) 3-hydroxy-4-methoxy- after decolorizingwhite benzaldehyde, 0.44 g pH_(m) = 9.1 12.4 A11,2-dimethyl-5-methoxy-3- gray-green untreated hair +83.30  −0.48 +10.40(spirocyclohexyl)-3H-indolium- after dyeing tetrafluoroborate, 0.95 gA2) 3,4,5-trihydroxybenz- after decolorizing white aldehyde, 0.49 gpH_(m) = 8.4 12.5 A1 1,2-dimethyl-5-methoxy-3- pink untreated hair+83.30  −0.48 +10.40 (spirocyclohexyl-3H-indolium after dyeing +73.66+22.70  +6.04 tetrafluoroborate, 0.95 g A2) 4-(dimethylamino)- afterdecolorizing white benzaldehyde, 0.43 g pH_(m) = 9.2

[0210] The L*a*b* color measurements presented in the foregoing Tables 1to 11 were determined with a Chromameter II instrument supplied byMinolta.

[0211] In the foregoing, L stands for luminosity (namely the lower the Lvalue the higher is the color intensity), whereas a is a measure of thered content of the color (namely the higher the a value the greater isthe red content). The b value is a measure of the blue content of thecolor, the blue content being the greater the more negative the b value.

1. Agent for dyeing fibers obtained by mixing two components, ifnecessary with the addition of an alkalinizing agent or an acid,characterized in that one component (component A2) contains at least onecarbonyl compound and the other component (component A1) contains atleast one indoline derivative of formula (I) or a 3H-indoline derivativeof formula (Ia)

the R1 to R8 and A⁻ groups in the formulas (I) and (Ia) having thefollowing meaning: R1 denotes a straight-chain or branched C1-C8 alkylgroup, C1-C8 monohydroxyalkyl group, C2-C8 polyhydroxyalkyl group, C1-C8alkoxy-(C1-C8)-alkyl group or a thio-(C1-C8)-alkyl group, a—(CH₂)_(n)—X—R^(a) group, a —(CH₂)_(m)—X—(CH₂)_(n)—Y—(CH₂)_(p)—R^(a)group, a —(CH₂)_(p)—R^(a) group, a—(CH₂)_(m)—Y—(CH₂)_(n)—X—(CH₂)_(p)—R^(a) group, a—(CH₂)_(m)—CO—(CH₂)_(p)—X—R^(a) group, a—(CH₂)_(m)—X—(CH₂)_(p)—CO—Y—R^(a) group or

 wherein X and Y independently of each other denote an oxygen atom, asulfur atom or an NR^(b g)group, R^(a) and R^(b) independently of eachother denote a hydrogen atom, an, optionally substituted, aromaticcarbocycle or heterocycle or a straight-chain or branched C1-C8-alkylgroup, m and n independently of each other denote an integer from 1 to 6and p denotes an integer from 0 to 6; R2 is a hydrogen atom or astraight-chain C1to C6-alkyl group, R3 and R4 independently of eachother denote a straight-chain or branched C1-C4-alkyl group, a(CH₂)_(n)R^(c) group, a —(CH₂)_(m)—CHR^(c)—X—(CH₂)_(n)—R^(c) group, a—(CH₂)_(n)—CO—R^(c) group, a —(CH₂)_(n)—CO—XR^(c) group, a —(CH₂)_(n)—CNgroup, a —(CH₂)_(n)—CH═C(CH₃)₂ group, a—(CH₂)_(m)—X—CHR^(c)(CH₂)_(n)—R^(c) group or a —(CH₂)_(n)CH═CH group, Xstanding for an oxygen atom, sulfur atom or an NR^(b) group, m and nindependently of each other denoting 1 to 6 and R^(c) standing for ahydrogen atom, an, optionally substituted, aromatic carbocycle orheterocycle or a straight-chain or branched C1-C6-alkyl group, providingthat the R3 and R4 groups, together, linked through a (CH₂)_(n) group(with n=1-3) can also form a spiro compound with the 3H carbon; R5, R6,R7 and R8 independently of each other denote a straight-chain orbranched C1-C4-alkyl group or a C1-C4-hydroxyalkyl group, a hydroxylgroup, a methoxy group, a benzyl group, a halogen atom, a nitro group, anitroso group, a cyano group, a trifluoromethyl group, a —CHO group, a—COR^(d) group, a —COOH group, a —CO₂R^(d) group, an —OCOR^(d) group, an—OCH₂-aryl group, an —SO₂NH₂ group, an —NH₂ group, an NH₃ ⁺ group, an—NHR^(d) group, an —NH₂R^(d)— group, an —N(R^(d))₂ group, an —N(R^(d))₃⁺ group, an —NHCOR^(d) group, an —NHCOOR^(d) group, a —CH₂NH₂ group, a—CH₂NHR^(d) group, a —CH₂N(R^(d))₂ group, a —CO₂CF₃ group, a—PO(OR^(d))₂ group, an —SO₂CHF₂ group, an —SO₂CF₃ group, an —SO₂R^(d)group or an —SR^(d) group, wherein R^(d) denotes a hydrogen atom, an,optionally substituted, aromatic carbocycle or a heterocycle or aC1-C6-alkyl group, providing that at least one of the R5 to R8 groups isdifferent from hydrogen; and A⁻ denotes an anion of an organic orinorganic acid.
 2. Agent according to claim 1, characterized in that thecompound of formula (I)/(Ia) is selected from among1,3,3,4-tetramethyl-2-methyleneindoline and the salts thereof,1,3,3,5-tetramethyl-2-methyleneindoline and the salts thereof,1,3,3,6-tetramethyl-2-methyleneindoline and the salts thereof,1,3,3,7-tetramethyl-2-methyleneindoline and the salts thereof,1,3,3,6,7-pentamethyl-2-methyleneindoline and the salts thereof,1,3,3,5,7pentamethyl-2-methyleneindoline and the salts thereof,1,3,3,4,7-pentamethyl-2-methyleneindoline and the salts thereof,5-fluoro-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,5-isopropyl-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,5-hydroxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,5-methoxy-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,5-nitro-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,5-amino-1,3,3-trimethyl-2-methyleneindoline and the salts thereof,5-N-acetylamino-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof, 6-hydroxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof, 6-methoxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof, 5-methoxy-6-nitro-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof, 5-methoxy-6-amino-1,3,3-trimethyl-2-methyleneindoline andthe salts thereof,5-methoxy-6-N-acetylamino-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof, 5,6-dihydroxy-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof, 5,6-dimethoxy-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof, 5,6-methylenedioxy-1,3,3-trimethyl-2-methyleneindolineand the salts thereof, 4,5-dihydroxy-1,3,3-trimethyl-2-methyleneindolineand the salts thereof, 5,7-dihydroxy-1,3,3-trimethyl-2-methyleneindolineand the salts thereof,5-amino-6-methoxy-1,3,3-trimethyl-2-methyleneindoline and the saltsthereof, 5-amino-7-hydroxy-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof, 5-hydroxy-7-amino-1,3,3-trimethyl-2-methyleneindoline andthe salts thereof,5-hydroxy-7-N-acetylamino-1,3,3-trimethyl-2-methyleneindoline and thesalts thereof, 1-methyl-3-spirocyclopropyl-2-methyleneindoline and thesalts thereof, 1-methyl-3-spirocyclohexyl-2-methyleneindoline and thesalts thereof, 1-methyl-3-spirocyclohexyl-5-hydroxy-2-methyleneindolineand the salts thereof and1-methyl-3-spirocyclohexyl-5-methoxy-2-methyleneindoline and the saltsthereof.
 3. Agent according to claim 1 or 2, characterized in that thecarbonyl compound is selected from among vanillin, isovanillin,3,4-dihydroxybenzaldehyde, 4-hydroxybenzaldehyde,3,5-dimethoxy-4-hydroxybenzaldehyde, 4-dimethylaminobenzaldehyde,4-methyl-5-imidazolecarboxaldehyde, 4-dimethylaminocinnamaldehyde,4-hydroxy-2-methoxybenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde,4-dimethylamino-2-methoxybenzaldehyde, 2-hydroxybenzaldehyde,4-hydroxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde,4-dimethylamino-1-naphthaldehyde, 4′-hydroxybiphenyl-1-carboxaldehyde,2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde,3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde,2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde,2,4,6-trihydroxybenzaldehyde, 2,4-dimethoxybenzaldehyde,2,3-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde,3,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde,indole-3-carboxaldehyde, benzene-1,4-dicarboxaldehyde,4-ethoxybenzaldehyde, 2-methyl-1,4-naphthoquinone,4-carboxybenzaldehyde, 4-hydroxy-3-methoxycinnamaldehyde,3,5-dimethoxy-4-hydroxycinnamaldehyde,3-methoxy-4-(1-pyrrolidinyl)benzaldehyde,4-diethylamino-3-methoxybenzaldehyde, 1,2,-phthalaldehyde,pyrrole-2-aldehyde, thiophene-2-aldehyde, thiophene-3-aldehyde,chromone-3-carboxaldehyde, 6-methyl-4-oxo-1(4H)-benzopyran-3-carboxaldehyde, N-methylpyrrole-2-aldehyde,5-methylfufural, 6-hydroxychromene-3-carboxaldehyde,6-methyl-indole-3-carboxaldehyde, 4-dibutylaminobenzaldehyde,N-ethylcarbazole-3-aldehyde, 4-diethylamino-2-hydroxybenzaldehyde,3,4-dimethoxy-5-hydroxybenzaldehyde,5-14-(diethylamino)phenyl)-2,4-pentadienal, 2,3-thiophenecarboxaldehyde,2,5-thiophenedicarboxaldehyde, 2-methoxy-1-naphthaldehyde,3-ethoxy-4-hydroxybenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehydeand 4-nitrobenzaldehyde.
 4. Agent according to one of claims 1 to 3,characterized in that the total amount of the compound of formula (I) or(Ia) contained in component A1 is about 0.02 to 20 weight percent. 5.Agent according to one of claims 1 to 4, characterized in that the totalamount of the carbonyl compound contained in component A2 is about 0.02to 20 weight percent.
 6. Agent according to one of claims 1 to 5,characterized in that the total amount of the compound of formula (I) or(Ia) and the carbonyl compound contained in the ready-for-use colorantobtained by mixing components A1 and A2 is about 0.01 to 10 weightpercent.
 7. Agent according to one of claims 1 to 6, characterized inthat it contains additionally at least one direct dye.
 8. Agentaccording to one of claims 1 to 7, characterized in that the pH of theready-for-use colorant Is between 3 and
 11. 9. Multicomponent kit fordyeing and later decolorizing fibers, characterized in that it containsa colorant (A) according to one of claims 1 to 8 and at least onesulfite-containing, decolorizing component (B).
 10. Multicomponent kitaccording to claim 9, characterized in that the decolorizing agent (B)has a pH of 3 to 8.